title: Crystal-field analysis and calculation of two-photon absorption line strengths of dicesium sodium hexachlorogadolinate(III).
abstract: The crystal-field energy level calculation of the 4f(7) ion Gd(3+) in the crystal Cs(2)NaGdCl(6) has fitted 45 levels with standard deviation 12 cm(-1), with the energy parameters being consistent with those from other studies. The resulting eigenvectors have been employed in the calculation of two-photon absorption (TPA) intensities of transitions from the electronic ground state (8)S(7/2) to the crystal-field levels of excited (6)P, (6)I and (6)D multiplet terms. The TPA line strengths are highly polarization dependent and exhibit striking differences for linearly polarized incident radiation compared with circularly polarized radiation. The relative intensities are compared with those available from previous experimental studies and some reassignments have been made. Good agreement of calculated and experimental TPA spectra is found, except for the intensity ratio of the transitions to (6)P(7/2) or (6)P(5/2) compared with that to (6)P(3/2), for linear and circular polarizations, where the calculation overestimates the ratio. Reasons for this disagreement are presented.
authors.affiliation: Department of Biology and Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong SAR, People's Republic of China.
authors.forename: Chang-Kui
authors.initials: CK
authors.lastname: Duan
authors.forename: Peter A
authors.initials: PA
authors.lastname: Tanner
mesh_terms: D002586:Cesium / Q000737:chemistry*; D003460:Crystallization; D005682:Gadolinium / Q000737:chemistry*; D007477:Ions; D008422:Materials Testing; D008968:Molecular Conformation; D010825:Physics / Q000379:methods; D012964:Sodium / Q000737:chemistry*; D013696:Temperature
chemical_list: D007477:Ions; D002586:Cesium; D012964:Sodium; D005682:Gadolinium